KR102086051B1 - Copolycarbonate and molded article prepared by using the same - Google Patents

Abstract

The present invention relates to a copolycarbonate having excellent mechanical properties but also excellent fluidity and transparency, and a molded article produced using the same.

Description

COPOLYCARBONATE AND MOLDED ARTICLE PREPARED BY USING THE SAME}

The present invention relates to a copolycarbonate having excellent mechanical properties but also excellent in fluidity and transparency, and a method for preparing the same.

Polycarbonate resin is a polymer material that is used in various fields such as exterior materials, automotive parts, building materials, optical parts, etc. of electrical and electronic products due to excellent properties such as impact strength, numerical stability, heat resistance and transparency.

As polycarbonate resins have recently been expanded in application fields, there is a need for development of a copolycarbonate having a novel structure having improved fluidity and transparency while maintaining physical properties of polycarbonate resins.

Accordingly, studies have been attempted to copolymerize two or more different types of aromatic diols to introduce units having different structures into the main chain of polycarbonate to obtain desired physical properties. However, most of the technologies have a high production cost, and if the chemical resistance or impact strength is increased, the transparency is lowered, and if the transparency is improved, the chemical resistance or impact strength is lowered.

Accordingly, there is still a need for research and development on copolycarbonates having excellent mechanical properties such as impact strength and excellent fluidity and transparency.

The present invention is to provide a copolycarbonate excellent in mechanical properties, but also excellent in fluidity and transparency, and a molded article manufactured using the same.

The present invention includes a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), wherein the repeating unit represented by the formula (1) comprises 0.1 to 1 parts by weight relative to the repeating unit represented by the formula (2), It provides a copolycarbonate, the melt index (MI) is more than the value according to the following equation (1).

The present invention also provides a molded article made of the copolycarbonate.

Hereinafter, a copolycarbonate according to a specific embodiment of the present invention, and a molded article will be described in more detail.

According to an embodiment of the invention, the repeating unit represented by the following formula (1) and the repeating unit represented by the formula (2), the repeating unit represented by the formula (1) is 0.1 to 1 weight relative to the repeating unit represented by the formula (2) Wealth included

Copolycarbonates can be provided in which the melt index (MI) is greater than or equal to the value according to Equation 1:

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

X is Beach and unsubstituted or phenyl-substituted C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, or CO, the

n is an integer from 1 to 20,

[Formula 2]

In Chemical Formula 2,

R ₅ to R ₈ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Z is Beach and unsubstituted or phenyl-substituted C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, or CO, the

[Equation 1]

8 * 10 ²¹ * X ^-4.645

In Equation 1,

X is the weight average molecular weight of the said copolycarbonate, and is 23,000-40,000.

In particular, the copolycarbonate of the embodiment includes 0.1 to 1 parts by weight of the repeating unit represented by Formula 1 compared to the repeating unit represented by Formula 2. As such, by including the repeating unit represented by the formula (1) in the above range, it is possible to improve the transparency and the melt index of the copolycarbonate. More specifically, when the content of the repeating unit represented by Chemical Formula 1 exceeds 1 part by weight, impact resistance and glass transition temperature may be lowered, and when included in less than 0.1 part by weight, the melt index is small compared to the molecular weight, transparency This can be degraded.

In addition, the copolycarbonate of the embodiment is characterized in that the melt index (MI) is more than the value according to Equation 1 related to the weight average molecular weight. In this case, the weight average molecular weight may use a value measured using a GPC device, the melt index may use a value measured using a MI measurement device, and the relationship is expressed by inserting a trend line by graphing them. Can be derived.

Copolycarbonate of one embodiment satisfying such a relationship can be selectively improved fluidity and transparency while maintaining the inherent properties such as high glass transition temperature, impact resistance of the general polycarbonate resin, light guide plate, car lamp It can be applied to LED lamp related fields.

More specifically, the copolycarbonate may have a melt index (MI) greater than or equal to the value according to Equation 1, preferably greater than or equal to the value according to Equation 1 and less than or equal to the value according to Equation 2 below.

[Equation 2]

9 * 10 ¹⁹ * X ^-4.18

In Equation 2,

X is the weight average molecular weight of the said copolycarbonate, and is 23,000-40,000.

In Formula 1, n is preferably an integer of 3 to 10.

Also preferably, R ₁ to R ₄ are each independently hydrogen, methyl, chloro, or bromo. Also preferably, X is straight or branched C _1-10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, Butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, X is cyclohexane-1,1-diyl, O, S, SO, SO ₂ , or CO.

More preferably, the repeating unit represented by Formula 1 is represented by the following Formula 1-1:

[Formula 1-1]

.

.

In addition, in Formula 2, preferably, R ₅ to R ₈ are each independently hydrogen, methyl, chloro, or bromo. Also preferably, Z is straight or branched C _1-10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, Butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, Z is cyclohexane-1,1-diyl, O, S, SO, SO ₂ , or CO.

More preferably, the repeating unit represented by Formula 2 is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy Phenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (4- Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4 -Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl)- From the group consisting of 1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, and α, ω-bis [3- (ο-hydroxyphenyl) propyl] polydimethylsiloxane Selection can be derived from any one or more aromatic diol compounds.

The term “derived from an aromatic diol compound” means that a hydroxyl group of an aromatic diol compound reacts with a carbonate precursor to form a repeating unit represented by Chemical Formula 2.

For example, when bisphenol A, an aromatic diol compound, and triphosgene, a carbonate precursor, are polymerized, the repeating unit represented by Formula 2 is represented by the following Formula 2-1.

[Formula 2-1]

.

.

Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, One or more selected from the group consisting of bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishaloformates can be used. Preferably, triphosgene or phosgene can be used.

In addition, the copolycarbonate may have a glass transition temperature of 143 ° C or higher, preferably 144 ° C or higher, more preferably 145 ° C or higher. The copolycarbonate of the embodiment may exhibit a high glass transition temperature by including 0.1 to 1 parts by weight of the repeating unit represented by Formula 1 compared to the repeating unit represented by Formula 2, but the repeating unit represented by Formula 1 is 1 When the amount is more than 1.5 parts by weight, the glass transition temperature may be lowered to 143 ° C. or less.

In addition, the copolycarbonate may have an impact strength of 500 J / m or more, preferably 550 J / m, more preferably 600 J / m. Similar to the glass transition temperature, the copolycarbonate of the embodiment may exhibit a high impact strength by including 0.1 to 1 parts by weight of the repeating unit represented by Formula 1 compared to the repeating unit represented by Formula 2, If the repeating unit represented by more than 1 part by weight, for example, including 1.5 parts by weight or more, the impact strength may be lowered to 500 J / m or less.

On the other hand, the copolycarbonate of one embodiment may be prepared by polymerizing a composition comprising a compound represented by the following formula (3), an aromatic diol compound and a carbonate precursor:

[Formula 3]

In Chemical Formula 3,

R ^' is hydrogen, OH, C _1-10 alkyl, or halogen.

In this case, the compound represented by Formula 3 is 0.05 part by weight or more, or 0.1 part by weight or more, 2 parts by weight or less, 1 part by weight, or 0.5 part by weight or less based on 100 parts by weight of the aromatic diol compound. can do. By adjusting the content of the formula (3) in the polymerization step as described above, the weight ratio of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) can be adjusted, by mixing the compound represented by the formula (3) in the above range It is possible to improve the melt index of the copolycarbonate produced.

In addition, the aromatic diol compound and the carbonate precursor are as described above in the aromatic diol compound and the carbonate precursor that can be used to form the repeating unit of Formula 2.

In addition, the polymerization is preferably performed by interfacial polymerization, and the polymerization reaction is possible at atmospheric pressure and low temperature during interfacial polymerization, and molecular weight is easily controlled.

The polymerization temperature is preferably 0 ° C to 40 ° C, and the reaction time is 10 minutes to 5 hours. In addition, it is preferable to maintain pH at 9 or more or 11 or more during reaction.

As a solvent which can be used for the said superposition | polymerization, if it is a solvent used for superposition | polymerization of copolycarbonate in the art, it will not specifically limit, For example, halogenated hydrocarbons, such as methylene chloride and chlorobenzene, can be used.

In addition, the polymerization is preferably carried out in the presence of an acid binder, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or an amine compound such as pyridine may be used as the acid binder.

In addition, in order to control the molecular weight of the copolycarbonate during the polymerization, it is preferable to polymerize in the presence of a molecular weight regulator. C _1-20 alkylphenol may be used as the molecular weight regulator, and specific examples thereof include p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, and eico. Silphenol, docosylphenol or triacontylphenol. The molecular weight modifier may be added before the start of the polymerization, during the start of the polymerization or after the start of the polymerization. The molecular weight modifier is, for example, 0.01 part by weight, 0,1 part by weight, or 1 part by weight or more, 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less, based on 100 parts by weight of the aromatic diol compound. Preferably, 0.1 to 6 parts by weight can be used, and the desired molecular weight can be obtained within this range.

In addition, in order to promote the polymerization reaction, reactions such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compounds, quaternary phosphonium compounds and the like Accelerators may further be used.

According to another embodiment of the invention, a molded article made of the copolycarbonate may be provided. As described above, the copolycarbonate including the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 has excellent mechanical properties such as impact strength, but the melt index (MI) is related to the weight average molecular weight. The fluidity is also improved, such as showing a higher value than the value, so that the field of application is wider than that of a conventional molded product made of polycarbonate.

The molded article is at least one selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent brighteners, ultraviolet absorbers, pigments and dyes, if necessary, in addition to the copolycarbonate according to the present invention. It may further include.

As an example of the method for producing the molded article, the copolycarbonate and other additives according to the present invention are mixed well using a mixer, and then extruded into an extruder to produce pellets, and the pellets are dried and then injected into an injection molding machine. It may include a step.

According to the present invention, a copolycarbonate having excellent mechanical properties but also excellent fluidity and transparency can be provided and a molded article manufactured using the same.

1 is a graph showing the relationship of the melt index (MI) with respect to the weight average molecular weight of Examples, Comparative Examples copolycarbonate.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Example: Preparation of Copolycarbonate

Example 1

2L main reactor equipped with nitrogen purge and condenser and maintained at room temperature with circulator H ₂ O 620g, BPA 116.47g, Sebacoyl chloride 0.312ml (0.3 wt% compared with BPA), NaOH 102.5g, MeCl ₂ 200ml Was added and stirred for a few minutes.

Stop nitrogen purging, add 62 g of Triphosgene and 120 g of MeCl ₂ in a 1 L round-bottom flask, dissolve the Triphosgen, and slowly add the dissolved Triphosgen solution to the main reactor in which the BPA solution is dissolved. The mixture was stirred for 10 minutes. After stirring was completed, 97 g of 40 wt% NaOH aqueous solution was added thereto, and then 1.16 g of TEA was added as a coupling agent. At this time, the reaction pH was maintained at 11 to 13. In order to complete the reaction, the pH was lowered to 3-4 by adding HCl to terminate the reaction. Then, the stirring was stopped to separate the polymer layer and the water layer, the water layer was removed, and pure H ₂ O was added again and washed with water for three to five times. After complete washing with water, only the polymer layer was extracted, and polymer crystals were obtained by reprecipitation using a nonsolvent using methanol, H ₂ O, or the like.

At this time, the produced copolycarbonate had a weight average molecular weight of 31,000 g / mol.

Example 2

Copolycarbonate was prepared in the same manner as in Example 1, except that the content of sebacoyl chloride was changed to 0.104 ml (0.1 wt% of BPA).

Example 3

Copolycarbonate was prepared in the same manner as in Example 1, except that the content of sebacoyl chloride was changed to 0.52 ml (0.5 wt% compared to BPA).

Example 4

Copolycarbonate was prepared in the same manner as in Example 1, except that the content of sebacoyl chloride was changed to 1.04 ml (1 wt% of BPA).

Example 5

Copolycarbonate was prepared in the same manner as in Example 1, except that the amount of PTBP was changed to 3.41 g.

Example 6

Copolycarbonate was prepared in the same manner as in Example 1, except that the amount of PTBP was changed to 1.97 g.

Comparative Example 1

Copolycarbonate was prepared in the same manner as in Example 1, except that the use of PTBP was changed to 3.41 g without using sebacoyl chloride.

Comparative Example 2

A copolycarbonate was prepared in the same manner as in Example 1, except that sebacoyl chloride was not used.

Comparative Example 3

Copolycarbonate was prepared in the same manner as in Example 1, except that PTBA was not changed to 1.97 g without using sebacoyl chloride.

Comparative Example 4

Copolycarbonate was prepared in the same manner as in Example 1, except that the content of sebacoyl chloride was changed to 0.052 ml (0.05 wt% compared to BPA).

Comparative Example 5

A copolycarbonate was prepared in the same manner as in Example 1, except that the content of sebacoyl chloride was changed to 1.27 ml (1.5 wt% of BPA).

Comparative Example 6

Copolycarbonate was prepared in the same manner as in Example 1, except that the content of sebacoyl chloride was changed to 3.12 ml (3 wt% of BPA).

Comparative Example 7

A copolycarbonate was prepared in the same manner as in Example 1, except that the content of sebacoyl chloride was changed to 7.28 ml (7 wt% of BPA).

Experimental Example: Evaluation of Physical Properties of Copolycarbonate

The characteristics of the injection specimens of the copolycarbonate resins prepared in Examples 1 to 6 and Comparative Examples 1 to 7 were measured by the following method, and the results are shown in Table 1 below.

* Weight average molecular weight (g / mol): Agilent 1200 series was measured by calibration with PC standard.

* Melt index (flowability, MI): measured according to ASTM D1238 (300 DEG C, 1.2 kg conditions).

* Glass transition temperature (Tg, ℃): was measured using a differential scanning calorimetry (Differential Scanning Calorimetry, DSC).

* Impact strength: measured at room temperature according to ASTM D256 (1/8 inch, Notched Izod).

* transmittance (Tt): Tt was measured by irradiating light of 380 to 780 nm using a Spectrophotometer U-4100 (Hitachi Co., Ltd.).

* Yellow Index (YI): Based on ASTM D1925, Color-Eye 7000A (X-rite, Inc.) was measured by measuring the transmittance at room temperature, Spectral range (360 to 750 nm).

Mw
(g / mol) MI
(g / 10min) Tg
(℃) Izod Impact
(J / m) Tt
(%) YI Example 1 31,000 14 150.1 746 90.52 0.96 Example 2 31,000 12.9 150.5 757 90.42 0.97 Example 3 31,000 14.2 147.8 744 90.84 0.94 Example 4 31,000 14.8 145.5 739 91.14 0.93 Example 5 24,700 34 148.8 630 90.62 0.96 Example 6 34,900 9 149.6 869 90.44 0.98 Comparative Example 1 24,700 26.2 151.2 645 90.33 1.2 Comparative Example 2 31,000 10.8 151.6 784 90.1 1.3 Comparative Example 3 34,900 5.7 151.8 870 89.66 1.7 Comparative Example 4 31,000 10.9 150.8 778 90.1 1.11 Comparative Example 5 31,000 15.8 142.5 482 91.16 0.92 Comparative Example 6 31,000 16.3 140.1 412 91.32 0.92 Comparative Example 7 31,000 17.2 132.5 352 91.53 0.92

As shown in Table 1, the copolycarbonates of Examples 1 to 6 containing 0.1 to 1 parts by weight of repeating units derived from Sebacoyl chloride compared to repeating units derived from BPA are copolycarbonates containing no repeating units derived from Sebacoyl chloride. It can be seen that the melt index at the same weight average molecular weight is higher than that of carbonate, and the transparency is excellent.

In addition, the copolycarbonates of Examples 1 to 6 contain 0.1 to 1 parts by weight of repeating units derived from Sebacoyl chloride, compared to BPA derived repeating units, and 1.5 parts by weight or more of repeating units derived from Sebacoyl chloride of Comparative Examples 5 to 7 It was confirmed that the glass transition temperature of 145 ° C. or higher and the impact strength of 600 J / m or higher were higher than those of the copolycarbonates included.

Claims (9)

To include a repeating unit represented by the formula (1-1) and a repeating unit represented by the formula (2), the repeating unit represented by the formula (1-1) comprises 0.1 to 1 parts by weight relative to the repeating unit represented by the formula (2),
Melt index (MI) is greater than or equal to the value according to Equation 1 below,
Copolycarbonates having a glass transition temperature of at least 145 ° C. and an impact strength of at least 600 J / m:
[Formula 1-1]

[Formula 2]

In Chemical Formula 2,
R ₅ to R ₈ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
Z is Beach and unsubstituted or phenyl-substituted C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, or CO, the
[Equation 1]
8 * 10 ²¹ * X ^-4.645
[Equation 2]
9 * 10 ¹⁹ * X ^-4.18
In Equations 1 and 2,
X is the weight average molecular weight of the said copolycarbonate, and is 23,000-40,000.
delete delete delete The method of claim 1,
The repeating unit represented by the formula (2) is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide , Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (4-hydroxyphenyl) Butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy- 3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2- Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane , Bis (4-hydroxyphenyl) diphenylmethane, and α, ω-bis [3- (ο-hydroxyphenyl) propyl] polydimethylsiloxane A copolycarbonate, which is derived from one or more aromatic diol compounds.
The method of claim 1,
Formula 2 is represented by the formula 2-1, Copolycarbonate:
[Formula 2-1]

.
delete delete A molded article made of the copolycarbonate of any one of claims 1, 5 and 6.

Images